The Assignment of the Absolute Configuration of C-22 Chiral Center in the Aglycones of Triterpene Glycosides from the Sea Cucumber Cladolabes schmeltzii and Chemical Transformations of Cladoloside C
Free accessResearch articleFirst published online July, 2015
The Assignment of the Absolute Configuration of C-22 Chiral Center in the Aglycones of Triterpene Glycosides from the Sea Cucumber Cladolabes schmeltzii and Chemical Transformations of Cladoloside C
The absolute R-configuration of the C-22 chiral center in cladoloside C (1) and therefore in all related glycosides isolated from the sea cucumber Cladolabes schmeltzii has been assigned by Mosher‘s method. Some chemical transformations of the native glycoside 1 were carried out to apply this method. This resulted in the isolation and elucidation of chemical structures of progenin 2 and artefact aglycones 3 and 4, obtained from 1 and assignment of the absolute R-configuration of C-22 in the progenin 2. The coincidence of C-22 configurations in the studied compounds with those of the earlier known lanostane-type aglycone of frondoside C and holostane-type aglycone of cladoloside C (1) confirms the generic biosynthetic pathways to different types of sea cucumber glycoside aglycones. It suggests the same R-configuration of C-22 chiral centers in all the sea cucumber glycosides having C-22 functionalities.
SilchenkoAS, KalinovskyAI, AvilovSA, AndryjascchenkoPV, DmitrenokPS, YurchenkoEA, DolmatovIY, KalininVI, StonikVA. (2013) Structure and biological action of cladolosides B1, B2, C, C1, C2 and D, six new triterpene glycosides from the sea cucumber Cladolabes schmeltzii. Natural Product Communications, 8, 1527–1534.
2.
SilchenkoAS, KalinovskyAI, AvilovSA, AndryjascchenkoPV, DmitrenokPS, YurchenkoEA, DolmatovIY, SavchenkoAM, KalininVI. (2014) Triterpene glycosides from the sea cucumber Cladolabes schmeltzii. II. Structure and biological action of cladolosides A1–A6. Natural Product Communications, 9, 1421–1428.
3.
SilchenkoAS, KalinovskyAI, AvilovSA, AndryjascchenkoPV, DmitrenokPS, YurchenkoEA, DolmatovIY, SavchenkoAM, KalininVI. (2015) Structures and biological activities of cladolosides C3, E1, E2, F1, F2, G, H1 and H2, eight triterpene glycosides from the sea cucumber Cladolabes schmeltzii with new carbohydrate chains. Carbohydrate Research, MS No. CAR-D-15-00065, in press.
4.
SecoJM, QuinoaE, RigueraR. (2004) The assignment of absolute configuration by NMR. Chemical Reviews, 104, 17–117;
5.
OhtaniI, KusumiT, KashmanY, KakisawaH. (1991) High-field FT NMR application of Mosher's method. The absolute configurations of marine terpenoids. Journal of the American Chemical Society, 113, 4092–4096;
6.
SuB-N, ParkEJ, MbwamboZH, SantarsieroBD, MesecarAD, FongHHS, PezzutoJM, KinghornD. (2002) New chemical constituents of Euphorbia quinquiecostata and absolute configuration assignment by a convenient Mosher ester procedure carried out in NMR tubes. Journal of Natural Products, 65, 1278–1282.
7.
OleinikovaGK., KuznetsovaTA, KalinovskyAI, StonikVA, ElyakovGB. (1981) Holothurin A1 – new triterpene glycoside from the sea cucumber Holothuria floridana. Khimiya Prirodnykh Soedinenij, 1, 101–102.
8.
OleinikovaGK, KuznetsovaTA, IvanovaNS, KalinovskyAI, RovnykhNV, ElyakovGB. (1982) The glycosides of marine invertebrates. XV. New triterpene glycoside – holothurin A1 from Caribbean sea cucumbers of the family Holothuriidae. Khimiya Prirodnykh Soedinenij, 4, 464–469.
9.
SunGQ, LiL, YiYH, YuanWH, LiuBS, WengYY, ZhangSL, SunP, WangZL. (2008) Two new cytotoxic nonsulfated pentasaccharide holostane (=20-hydroxylanostan-18-oic acid γ-lactone) glycosides from the sea cucumber Holothuria grisea. Helvetica Chimica Acta, 91, 1453–1460.
10.
BhatnagarS, DudoetB, AhondA, PoupatC, ThoisonO, ClastresA, LaurentD, PotierP. (1985) Invertebres marins du lagon neocaledonien IV. Saponines et sapogenines d'une holothurie, Actinopyga flammea. Bulletin de la Societe Chimique de France, 1, 124–129.
11.
ZhangSL, LiL, SunP, YiYH. (2008) Lecanorosides A and B, two new triterpene glycosides from the sea cucumber Actinopyga lecanora. Journal of Asian Natural Product Research, 10, 1097–1103.
12.
SilchenkoAS, StonikVA, AvilovSA, KalininVI, KalinovskyAI, ZaharenkoAM, SmirnovAV, MolloE, CiminoG. (2005). Holothurins B2, B3 and B4, New triterpene glycosides from Mediteranean sea cucumbers of the genus Holothuria. Journal of Natural Products, 68, 564–567.
13.
AfiyatullovSS. (1985) The isolation, determination of chemical structure and the investigation of chemical properties of triterpene glycosides from the Far Eastern sea cucumber Cucumaria fraudatrix. Ph. D. Dissertation. Vladivostok, Pacific Institute of Bioorganic Chemistry.
14.
KalininVI, KalinovskyAI, StonikVA. (1987) Onekotanogenin – new triterpene genine from the sea cucumber Psolus fabricii. Khimiya Prirodnykh Soedinenij, 5, 674–678.
15.
KitagawaI, NishinoT, KobayashiM, MatsunoT, AkutsuH, KyogokuY. (1981) Marine natural products. VII. Bioactive triterpene-oligoglycosides from the sea cucumber Holothuria leucospilota Brandt (1). Structure of holothurin B. Chemical and Pharmaceutical Bulletin, 29, 1942–1950.
16.
AvilovSA, DrozdovaOA, KalininVI, KalinovskyAI, StonikVA, GudimovaEN, RigueraR, JimenezC. (1998) Frondoside C, a new nonholostane triterpene glycoside from the sea cucumber Cucumaria frondosa: structure and cytotoxicity of its desulfated derivative. Canadian Journal of Chemistry, 76, 137–141.
17.
SilchenkoAS, AvilovSA, AntonovAS, KalinovskyAI, DmitrenokPS, KalininVI, WoodwardC, CollinPD. (2005) Glycosides from the sea cucumber Cucumaria frondosa. IV. Structure of frondosides A2–4, A2–7, and A2–8, three new minor monosulfated triterpene glycosides. Canadian Journal of Chemistry, 83, 2120–2126.
18.
SilchenkoAS, AvilovSA, KalinovskyAI, DmitrenokPS, KalininVI, MorreJ, DeinzerML, WoodwardC, CollinPD. (2007) Glycosides from the North Atlantic sea cucumber Cucumaria frondosa V – Structures of five new minor trisulfated triterpene oligoglycosides, frondosides A7–1, A7–3, A7–4, and isofrondoside C. Canadian Journal of Chemistry, 85, 626–636.
19.
SilchenkoAS, KalinovskyAI, AvilovSA, AndryjaschenkoPV, DmitrenokPS, MartyyasEA, KalininVI, JayasandhyaP, RajanGC, PadmakumarKP. (2013) Structures and biological activities of typicosideds A1, A2, B1, C1 and C2, triterpene glycosides from the sea cucumbers Actinocucumis typica. Natural Product Communications, 8, 301–310.
